Sulfonamides related to n,n,n{40 -tetra allyl diphenylether-4,4{40 disulfonamide

ABSTRACT

The compounds:   IN WHICH: (A) R1, R2, R3, R4, R5, R6R7, and R8 are independently selected from the group consisting of hydrogen, fluorine, chloride, bromine, and lower alkyl; (B). A is   (C). R9 is   AN ALKYLENE GROUP HAVING 2-20 CARBON ATOMS, A CYCLOALKYLENE GROUP HAVING 3-10 CARBON ATOMS, A PHENYLENE GROUP, AN ALKARYL GROUP HAVING 7-10 CARBON ATOMS, OR AN ARALKYL GROUP HAVING 7-10 CARBON ATOMS; AND D. R10 and R11 are independently selected from a group consisting of hydrogen, lower alkyl, a cycloalkyl group having 3-10 carbon atoms, a phenyl group, an alkylaryl group having 710 carbon atoms, and an aralkyl group having 7-10 carbon atoms.

llnite Dighe et al.

tet 1 Dec. 24, W74

[ SULFONAMIIDES RELATED TO N,N,N-TETRA ALLYL DIPHENYLIETHERAA'lDlSULFONAMlDE [75-] Inventors: Shrikant V. Dighe, Silver Spring;

Richard W. Bush, Columbia, both of Md.

[73] Assignee: W. R. Grace & C0., New York,

[22] Filed: Nov. 6, 1972 21 Appl. No.: 303,848

[52] US. Cl. 260/556 AR, 260/47 UA, 260/79.3 MU, 260/543 R, 260/612 R 51 int. Cl. C07c 143/78 [58] Field of Search 260/556 AR [56] References Cited UNITED STATES PATENTS 3,725,476 4/1973 Blackwood et a] 260/556 AR Primary Examiner-Henry R. Jiles Assistant Examiner-S. D. Winters Attorney, Agent, or Firm-Elton Fisher; Kenneth E. Prince [57] ABSTRACT The compounds:

IIgCzCHCIIz l HzCzCHCHz 1 in which:

(3) R1, R2, R3, R4, R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, fluorine, chloride, bromine, and

lower alkyl; (b). A is iiio Rn SO2NRs-1 IO2S;

(0). R is 7 Claims, N0 Drawings CH1 CIIZCH:

CH2 CII CH:

0 sogc1,

BACKGROUND OF THE INVENTION d. R and R are independently selected from a a group consisting of hydrogen, lower alkyl, a cycloalkyl group having 310 carbon atoms, a phenyl group, an alkylaryl group having 710 carbon This invention is directed to; (a) N,N,NN'- 5 atoms, and an aralkyl group having 7l0 carbon tetrallyldiphenylether-4,4'-disulfonamide (TADEDS); atoms. In specially preferred embodiments of the (b) a number of related sulfonamides; and (c) the prepcompound of Embodiment A, supra: aration of such sulfonamides from diphenylether-4,4'- 1. R R R R R R R R R and R are hydisulfonyl chloride (DEDSC) or nuclear substituted drogen.

DEDSC and diallylamine. DEDSC is commercially 10 2. R R R R R R R-,, and R (i.e., R through available from National Polychemicals, Inc., Wilming- R are hydrogen and R is ton, Mass, and 4,4-disulfonyl chlorides of substituted diphenylethers can be readily prepared by obvious conventional methods including those recited hereinafter. l5

SUMMARY OF THE INVENTION 7 In summary this invention is directed to a compound 3. R through R are hydrogen, R and 1 1 are hydrohaving the formula gen, and R is R1 R2 R5 R5 IIzC CHCHz l l l l CH2CH=CH2 in which R R R R R R R and R are independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, and lower alkyl.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In a preferred embodiment of the compound of the above Summary R R R R R R R and R are hydrogen.

35 In another preferred embodiment (Embodiment A) this invention is directed to a compound having the fora. R R R R R R and R are independently selected from the group consisting of hydrogen, fluorine, chloride, bromine, and lower alkyl;

b. A is llho Rn an alkylene group having 220 carbon atoms, a cycloalkylene group having 310 carbon atoms, a phenylene group, an alkaryl group having 7-10 carbon atoms, or an aralkyl group having7-10 carbon atoms; and

- c. R is it Q) 4. R, through R,, are hydrogen and R is an alkylene group having about 2-12 carbon atoms.

R through R are hydrogen and R is CI-I (CH CH 6. R, through R are hydrogen, R is -CI-I (CH C- H and R and R are hydrogen.

In another preferred embodiment (Embodiment B) this invention is directed to a compound having the fora. R R R R R R R and R are independently selected from the group consisting of hydrogen, fluorine, chloride, bromine, and lower alkyl;

an alkylene group having 2-2() carbon atoms, a cycloalkylene group having 3-10 carbon atoms, a phenylene group, an alkaryl group having 710 carbon atoms, or an aralkyl group having 7-10 carbon atoms; and

R1 R1 R5 Rt; 1120 011011: l (311,011 (in;

Nms- -o G -so,-N lr- (111011: l n-mu (in,

R1 R! R1 R;

d. R,,, and R,, are independently selected from a in which R,, R R,,, R,,, R R,,, R,, and R,, are indepengroup consisting of hydrogen, lower alkyl, a cyclodently selected from the group consisting of hydrogen, alkyl group having 3-10 carbon atoms, a phenyl fluorine, chlorine, bromine, and lower alkyl; or (2) Ra R5 R2 R1 R1 R2 R5 R6 QC-$011013 i i l l crncn=cm blots-6 O --o-@-A-@-o-@som 11:0:01106 l l cmlr=cn, R1 Ra R: R4 R, Ra R B."

group, an alkylaryl group having 7-10 carbon in which; atoms, and an aralkyl group having 7-10 carbon a. R,, R R R R R R and R,, are independently atoms. selected from the group consisting of hydrogen, ln specially preferred embodiments of the compound fluorine, chloride, bromine, and lower alkyl, of EmbodimentB, supra: b. A is 1. R, through R,, are hydrogen. 1m l tn 2. R, through R,, are hydrogen, R is S0 -I IRoNOzS;

O 3. R, through R,, are hydrogen, R is 3 O an alkylene group having 2-20 carbon atoms, a cycloall kylene group having 3-10 carbon atoms, a phenylene group, an alkaryl group having 7-10 carbon atoms, or

H an aralkyl group having 7-10 carbon atoms; and

d. R,,, and R,, are independently selected from a group consisting of hydrogen, lower alkyl, a cycloalkyl group having 3-10 carbon atoms, a phenyl group, an alkylarly group having 7-10 carbon atoms, and an aralkyl group having 7-10 carbon atoms; and

and R,,, and R,, are hydrogen.

4. R, through R,, are hydrogen and R,, is an alkylene group having about 2-12 carbon atoms. 5.. R, through R,, are hydrogen and R is -Cl-l (CH ),CH,-. (B) a h quld polythrol component having molecules R1 through R8 are hydrogen R9 ls CH2(CH2)4C' containing at least two thiol groups per molecule.

H and R,,, and R,, are hydrogen.

In especially preferred embodiments of the composition of Embodiment D: 1. The curable composition contains a photocuring In another preferred embodiments (Embodiment C) this invention is directed to a compound having the formula rate accelerator.

2. The photocurable rate accelerator is selected from f a group consisting of aryl aldehyde, diary] ketone, (wus 0 S0 C1 triaryl phosphine, and a blend of a carbon tetrahai lide with a polynuclear aromatic hydrocarbon.

R3 R8 R7 3. The photocuring rate accelerator is present in an effective amount from about 0.05 to about 25 percent by weight of the curable composition. in which n 2, 3, 4 5 6 1 and s are p 4. The composition contains a member of the group dently selected from the group consisting of hydrogen, consisting f a fill pigment, mask, lightfluori Chlorine, bromine, and lower alkyl Provided scattering agent, plasticizer and anitoxidant in an that at least 1 of 1 through 8 is a g p other than effective amount equal to about 0.005 to about 500 drogen. parts per 100 parts of the photocurable composi- In as especially preferred embodiment of the comi pound of Embodiment C, each of R, through R,, is DETAILED DESCRIPTION OF THE INVENTION In another preferred embodi ent e The reaction of primary and secondary amines with this invention is di t d t a curable composition benzenesulfonyl chloride is well known to those skilled consisting essentially of an intimate of; (A) a comin the art and was used by Hinsberg to separate mixpound having the formula: (1) tures of primary, secondary, and tertiary amines. See;

(a) Reynold C. Fuson, Organic Chemistry," Edwards Brothers, Inc., Ann Arbor, Michigan, 1939, pp. 216-217; and (b) Ralph G. Shriner et al, The Systematic Identification of Organic Compounds, John Wiley & Sons, Inc., New York, N.Y., 1956, pp. 103.

We have found that a modification of this reaction can be used to prepare polyenes having the formulas set forth in the above Summary and in Embodiment B, supra, and in the embodiments (number l-6) listed under said Embodiment B which can then be reacted with a polythiol of the type taught, described, and used in U.S. Pat. Nos. 3,535,193 (161/88, R. W. Prince) and 3,578,614 (260/13, W. R. Wszolek) to prepare offset printing blankets and curable compositions (useful as adhesives and for coating surfaces (e.g., wooden surfaces, soft metal surfaces, and the like) to provide a coating which, after curing will protect the coated surfaces from the action of solvents, scratching, and the like. i

We have also found that a modification of this reaction can be used to prepare compounds having the formulas set forth in Embodiment A, supra, and in the embodiments (the embodiments number 1-6) listed under said Embodiment A.

The instant invention will be better understood by referring to the following specific but nonlimiting examples. It is understood that said invention is not limited by these examples which are offered merely as illustrations; it is also understood that modifications can be made without departing from the spirit and scope of the invention.

EXAMPLE 1 M'aterialsi I i 36.7 g (0.1 mole), Diphenyl ether-4,4-disulfonyl chloride 8.0 g (0.2 mole), Sodium hydroxide 20.0 g (0.2 mole), Diallylamine In a 500 ml., three-necked round bottom flask equipped with a reflux condenser, thermometer, addition funnel and a mechanically driven stirrer were placed 8.0 g of sodium hydroxide dissolved in 100 ml of water and 20.0 g of diallylamine. The resulting mixture was heated to 50C while stirring. Diphenyl ether disulfonyl chloride (DEDSC) dissolved in 200 ml. of tetrahydrofuran was added dropwise from the funnel. After a few ml. of the solution had been added, the temperautre rose to 55C. At this point heating was stopped and the rate of addition so adjusted as to maintain a temperature of 5055C during addition. After the addition was complete, the reaction mixture was refluxed for four hours and then allowed to cool to room temperature. The cold solution separated into two layers. It was added to a large excess (ca. 1 liter) of water with vigorous stirring. A white precipitate sep arated; said precipitate was collected on a filter and dried in vacuo at 50C. The thus dried material was recrystallized from tetrahydrofuran-pentane mixture.

The white recrystallized product melted sharply at 85-86C and weighed 42.5 g corresponding to a conversion (1 pass yield of 88% of theory). Said recrystallized product was identified as TADEDS by NMR (nuclear magnetic resonance).

EXAMPLE 2 A composition was prepared by admixing TADEDS prepared as in EXAMPLE 1, supra, with pentaerythritol tetrakis (3-mercaptopropionate) which is also known as pentaerythritol tetrakis (B-mercaptopro pionate) in a mole ratio of 1:1 and incorporating into said mixture 2% by weight of benzophenone (based on the weight of the TADEDS). The resulting mixture was melted, admixed thoroughly, and spread over a thin metal sheet to form a thin film (ca. 15-20 mil thick). The resulting film was cooled to room temperature and exposed to the light of a 4,000 watt Ascorlux pulsed xenon arc printing lamp through a photographic negative having an image thereon. Exposure time was 2.6 minutes, the xenon light being about 30 inches from the surface of the aforesaid resulting film. A cured image was present on the exposed areas of said resulting film when said resulting film was developed by washing with a suitable solvent (a mixture of acetone and water in a weight ratio of about 3 parts acetone per part of water). The unexposed portions of said resulting film were dissolved and washed away bythe solvent while the exposed portions of said resulting film were not dissolved (and not washed away) by said solvent. The resulting printing'plate was mounted on aprinting press using double-face pressure-sensitive tape and printing was carried out in the same way conventional metal photoengraved plates are employed. The printing results obtained were superior to those with conventional plates.

EXAMPLE 3 The general procedure of Example 2 was repeated, however, in this instance the procedure was modified by dissolving the resulting mixture of TADEDS, pentaerythritol tetrakis (3mercaptopropionate) and benzophenone (after said resulting mixture had been melted and cooled) in acetone, applying a film of said acetone solution to a thin sheet of metal, and drying said film of acetone solution (i.e., freeing said film of its acetone) to form a resulting film of the composition of Example 2, (TADEDS plus pentaerythritol tetrakis (3-mercaptopropionate) plus benzophenone) having a thickness of about 15 mils on the surface of the metal sheet.

When this film of said composition was exposed to actinic light from the Xenon are printing lamp (said light passing through a photographic negative as in, Example 2) and developed as in Example 2. The resulting printing plate was mounted on a printing press using double-face pressuresensitive tape and printing was carried out in the same way conventional metal photoengraved plates are employed. The printing results obtained were superior to those with conventional plates.

EXAMPLE 4 TADEDS (N,N,N',N'-tetrallyldiphenylether-4,4- disulfonamide) made by the procedure of Example 1 was admixed with pentaerythritol tetrakis (3-mercaptopropionate) in a mole ratio of 1:1 and 3% of benzophenone (based on the weight of the TADEDS) was added to the mixture which was then melted, admixed thoroughly, cooled to room temperature, and designated Composition 4.

Composition 4 was dissolved in acetone and the resulting solution was designated Composition 4-A.

Composition 4-A was coated on a fine-count laminated offset blanket carcass composed of 3 layers of square weave X 80 prestretched cotton fabric impregnated and adhered together with a butadieneacrylonitrile combining compound. Lamination of the carcass took place under heat and pressure. The carcass was coated on a spreading apparatus equipped with a movable doctor blade which ran over the surface to be coated. The coated material was immobile on the support table. After the sheet was coated, the doctor blade was moved out of the way, and the coating was dried (i.e., the acetone was evaporated therefrom). A dry (substantially acetone free) coating having a thickness oof 0.020 inch resulted. The thus formed dry coating was exposed to the light of a 4,000 watt Ascorlux pulsed xenon arc printing lamp made by the American Speed Light Corp. which was placed 30 inches above the surface. Total exposure given to all portions of the coated blanket was 2 minutes and 40 seconds, the actinic light having passed through a photographic negative. The thus exposed coating was developed by treating with a mixture of acetone and water to remove uncured material and to form a fully developed offset plate. Thereafter the blanket was removed from the apparatus, punched at either end to receive blanket hooks and wrapped around the cylinder ofa small offset printing press. The lithograph plate test copy was prepared with 11 densities ranging from full black to light gray.

8 in which;

(a) R, through R are hydrogen; (b) A is Rm R11 SO:I I-R-I I02SZ (c) R is R1 R2 R R0 mc=oncm l i cmon=crn \NO2S@O@SO:N/ 1120: 0110141 I l l cm on=cm R4 R3 Rs B? Each density was properly reproduced. Performance in in which; all respects equaled a conventionally coated offset (a) R through R were hydrogen; blanket. (b) A was 5 l ii Materials: SOZ NRU NOES; 36.7 g (0.1 mole) DEDSC c. R was 4.0 g (0.1 mole) Sodium hydroxide 9.9 g (0.05 mole) Methylene bis-aniline II In a l-liter, three-necked, round bottom flask 40 equipped with a condenser, thermometer, addition funnel, and a mechanically driven stirrer were placed 4.0 g of sodium hydroxide dissolved in 100 ml. of water and and 9.9 g of methylene bis-aniline dissolved in 100 ml. tetrahydrofuran. The stirred mixture was heated to 50C and a solution of 36.7 g DEDSC in 100 ml. tetrahydrofuran added dropwise at such a rate as to maintain a reaction temperature of 50-55C. After the addition was complete, the reaction mixture was refluxed for one hour and allowed to cool to room temperature. The cooled mixture was designated "Mixture 5-A.

A small sample of the cooled mixture (Mixture 5-A) was removed from the reaction flask, evaporated to dryness (i.e., until substantially free of solvent) under reduced pressure leaving a first residue. The first residue was extracted .with a small quantity of dilute (ca. 2 molar) aqueous hydrochloric acid solution, leaving an extracted residue behind. The extracted residue was dried under reduced pressure leaving a second residue behind. This second residue was identified by NMR and by its infrared spectrum as d. R and R were hydrogen.

EXAMPLE 6 The general procedure of Example 4, supra, was repeated. However, in this instance, the TADEDS'used in Example 4 was replaced with Product 5-8 (from Example 5, supra). The results obtained were indistinguishable from those of Example 4.

EXAMPLE 7 Materials:

36.7g (0.] mile) DEDSC 9.3g (0.08 mole) Hexamethylenediamine 3.2g (0.08 mole) Sodium Hydroxide In a l-liter, three-necked, round bottom flask equipped with a condenser, thermometer, additional funnel, and a mechanically driven stirrer were placed 9.3 g of hexamethylenediamine dissolved in ml of tetrahydrofuran and 3.2 g of sodium hydroxide dissolved in 100 ml of water. The stirred mixture was heated to 5055C. and 3.6 g of DEDSC dissolved in 100 ml of tetrahydrofuran was added dropwise to maintain the reaction temperature at 5560C. After the addition was complete, the reaction mixture was refluxed for one hour and allowed to cool to room temperature. The cooled mixture was designated Mixture 7-A.

A small sample of the cooled mixture (Mixture 7-A) was removed from the reaction flask, evaporated to dryness (i.e., until substantially free of solvent) under reduced pressure leaving a first residue. The first resi due was extracted with a small quantity of dilute (ca. 2 molar) aqueous hydrochloric acid solution leaving an extracted residue behind. The extracted residue was dried under reduced pressure leaving a dried residue behind. This dried residue was identified by NMR and by its infrared spectrum as l EXAMPLE 9 Run No. 1: Preparation ofCompound 9-A, said compound having the formula Iom (Inn pm oln G om om Gila CH3 Several batches of the above-identified Compound 9-A were prepared by:

l. Admixing 0.25 mole of 2,3,5,6-tetramethylphenol and 1 mole of NaOH (present as an aqueous solution analyzing about 36% NaOH) in a reaction flask having a reflux condenser, an entrance port, and a mechanically driven stirrer. Water was added as necessary to place the phenol in solution.

2. Adding 0.25 mole of l-bromo-2,3,5,6-tetramethylbenzene to the first mixture while stirring the rein which;

a. R through R are hydrogen (b) A is io l n S Oz--1 IR0N-OgS;

' c. R is CH (CH CH and d. R and R are hydrogen. A solution of 1.6 g (0.04 mole) of sodium hydroxide in 50 ml of water was added to Mixture 7-A in the reaction flask. The resulting mixture in said flask was heated to 5560C. Diallylamine (4 g, 0.04 mole) was added dropwise and the resulting reaction mixture refluxed for an hour, cooled to room temperature, added to 500 ml of water, and acidified with hydrochloric acid to pH 5-6 causing a white precipitate to form. The precipitate was separated by filteration and dried under reduced pressure. The thus dried precipitate, which was designated Product 7-B was identified by NMR and by its infrared specturm as in which;

a. R through R were hydrogen; (b) A'was.

I Bin R11 S O2-I I-RnI I-Og S;

C. R9 is and d. R and R were hydrogen.

EXAMPLE 8 65 Thegeneral procedure of Example 4 was repeated.

However, in this instance, the TADEDS of Example 4, supra, was replaced with Product 7-B (from Example 7, supra). The results were indistinguishable from those of Example 4.

sulting second mixture and heating said second mixture to maintain a vigorous reflux-after refluxing for about 2 hours the second mixture was cooled to about C.

3. A third mixture was formed by neutralizing the cooled mixture with dilute hydrochloric acid (ca. 6 normal) using litmus paper as indicator. The third mixture was cooled to about 15C.

4. The cooled third mixture was extracted with one half its volume of cool (ca. 15C.) ether (i.e., ethyl ether (C H OC HQ); the thus extracted third mixture was extracted with a second portion of cool ether, and the 2 portions of ether extract were combined and washed with cool water (ca. 15C.) using about one volume of water per 5 volumes of ether extract. The thus washed ether extract was dried with Drierite (anhydrous calcium sulfate). The resulting dried ether extracta solution of Compound 9-A in etherwas designated Fourth Mixture.

5. Said compound 9-A was recovered from the fourth mixture by distilling the ethyl ether from the fourth mixture.

CH3 CH3 CH3 CH by reacting of the above-described compound 9-A with chlorosulfonic acid by slowly adding 0.2 mole said Compound 9-A to 1 mole of cold (ca. 0C.) chlorosulfonic acid while stirring the resulting mixture and maintaining it at about 0C. The resulting mixture was maintaincd at about C. for about 3 hours and then poured over a kilogram of crushed ic. The resulting Compound 9-B separated out. The separated Compound 9-B was recovered and dried under vacuum at about 50C. Compound 9-B was characterized and identified by elemental analysis and by its NMR and infrared spectra.

Run No. 3: The general procedure of Runs Nos. 1 and 2 of this Example were repeated. However, in this instance, the procedure used in Run No. 2 was modified by replacing the chlorosulfonic acid with a mixture of 1 mole of fuming sulfuric acid (ca. free 80;, content) and l mole of PCl The resulting product (Compound 9-B) was recovered, dried, and identified as in said Run No. 2.

Run No. 4: The general procedure of Example I was repeated. However, in this instance the procedure was modified by replacing the DEDSC of Example 1 with Compound 9-B from Run No. 2 of Example 9. The product Compound 9-C was identified by elemental analysis, NMR, and its infrared spectrum as R R3 R5 R6 IIQC CHCII2 TABLE 1' M aterlal 5 1lgNC1IzCI12-NIT2 1I2N@-emo1n@-Nm 1 1 i-@r@i C II:

H CH3 in which R through R were each Cl-l Run No. 5: The general procedure of Example 2 was repeated. However, in this instance the TADEDS was replaced with Compound 9-C from Run No.4 of Example 9. The results were indistinguishable from those of Example 2.

Run No. 6: The general procedure of Example I was repeated. However, in this instance the procedure was modified by replacing the DEDSC of Example 1 with Compound 9-B from Run No. 3 of Example 9. The product Compound 9-C was identified by elemental analysis, NMR, and its infrared spectrum as in which R, through R were each --CH Run No. 7: The general procedure of Example 2 was repeated. However, in this instance the TADEDS was replaced with Compound 9-C from Run No.6 of Exampie 9. The results were indistinguishable from those of Example 2.

EXAMPLE 10 A series of runs was made using the general procedure of Example 5. However in each of these runs the I R0 R5 methylene bisaniline was replaced with an equal molar amount of one of the materials listed in Table l, below (making at least one run with each of said materials).

cmorbori:

8 1IN---CHzCHzNII t). IIIyCIIzCII NI[ (3H2 (III-I $112 10 HN--CII2CHzCHz1TIH CII3 In each instance a resulting intermediate compound having the formula and 3,856,858 U M b. A was TABLE it C u Rm R 01 InnA Column B in which R R and R were determined by the mate- I CH1 rial listed in Table I used to prepare said intermediate 021-15 compound which was isolated and identified by ele- I mental analysis, NMR, and its infrared spectrum. Thus, v -Br where the material in Table l was CsII7 -011 1 R was phenylene and R and R were hydrogen and Cl where the material in said table was C1 CH3 01 I HNCH2CHZCH:NH v I CH2 I I .CQHS CH; ('31 1| 0 -o1r Br R was CH CH CH R was C1 In each instance the product was identified by ele- I mental analysis, NMR, and its infrared spectrum as a CH3 compound (Compound l2-A) having the formula and R was r ti 1 12 I m 166 o -oo a l In each instance the intermediate was reacted with. in which R R R and R corresponded to the funcdiallylamine as in Example 5 to produce a product tion groups (other than OH) of the compound (subcompound having the formula stituted phenol) selected from Column A of Table II R6 R5 R2 R1 R1 R2 R5 R0 II-JCICJICH: I CIIQCIIIICII:

R7 R3 R3 Rl R1 Rri R9 R1 in which R through R were hydrogen and A, R R which was used to prepare the Compound l2-A and R and R were the same as in the intermediate com- R R and R corresponded to the functional groups pound from which the product compound was pre- (other than bromine) of the substituted bromobenzene pared. The intermediate and product compounds were selected from Column B of Table ll which was used to identified by elemental analysis and by their infrared prepare the Compound l2-A.

and NMR spectra. A number of runs were made repeating the general procedure of Run No. 2 Example 9. However, in each EXAMPLE 1 1 instance, the procedure was modified by using a Com- A series of runs were made using the general procev pound l2-A selected from the above-prepared group of dure of Example 4. However, in these runs theprocecompounds which were designated Compound l2-A.

dure was modified by replacing the TADEDS of Exam- In each instance the resulting product was identified ple 4 with the product compounds of Example 10 by elemental analysis, NMR, and its infrared spectrum (using one of said product compounds in each run). In as a compound (Compound 12-8) having the foreach instance the results were indistinguishable from mula those of Example 4.

R1 R2 R5 R0 EXAMPLE I2 I ci2s o- -s02oi A number of runs were made using the general procedure of Run No. l of Example 9. However, in each R4 a a R1 of runs the 2,3,5,6-tetramethyl phenol was replaced with a material listed in Column A of Table ll, and the in which each of R R R R R R R and R was lbromo-2,3,5,6-tetramethyl benzene was replaced the same as in the Compound I2-A from which the with a material listed in Column B of Table II. Compound l2-B was prepared.

EXAMPLE 13 The general procedure of Example 1 was repeated. However, in this instance the procedure was modified by making a series of runs in which the diphenyl ether- 4,4-disulfonyl chloride of Example 1 was replaced with a Compound l2-B from Example l2 (using one Compound 12-B in each run).

In each run the product (Compound l3-A) was identified by elemental analysis, NMR, and its infrared spectrum as in which R R R R R ,'R R and R were the same as in Compound 12-13 from which the Compound l3-A was prepared.

EXAMPLE 14 A series of runs was made using the general procedure of Example 4. However in each of these runs the procedure was modified by replacing the TADEDS with a Compound l3-A from Example 13 (using one Compound l3-A per run). In each instance the results of these runs were indistinguishable from those of Example 4.

EXAMPLE 15 A series of runs was made using the general procedure of Example 5. However, in each of these runs the methylene bis-aniline was replaced (on a mole basis) with one of the materials listed in Table I and in each run the DEDSC was replaced (on a mole'for mole basis) with a Compound 12-B prepared according to the in lb lIeC =CIIClI2 R7 R procedure of Example 12, supra, using one Compound 12-8 in each run and making sufficient runs to insure that each Compound 12-B was reacted with each of the materials listed in said Table I.

In each instance the resulting product was identified by elemental analysis, NMR, and its infrared spectrum as a compound (Compound IS-A) having the formula c. R R and R were determined by the material listed in Table I from which the particular Compound l5-A was prepared. For example, where the material in Table l was R was phenylene and R and R were hydrogen and 10 when the material in said table was EXAMPLE 16 A series of runs was made using the general procedure of Example 1. However in these runs the procedure was modified by replacing, in each instance, the DEDSC with an equal molar amount of a Compound 35 l5-A (using one Compound lS-A in each run and making at least one run with each Compound l5-A).

In each instant the resulting product was identified by elemental analysis, NMR, and its infrared spectrum as a compound (Compound 16-A) having the formula and R was I'M R R and R are as in the particular Compound l5-A from which the particular Compound l6-A was prepared.

CllzClI Cll:

EXAMPLE 1? A series of runs were made using the general procedure of Example 4. However in each of these runs the procedure was modified by replacing the TADEDS with an equal molar amount of a Compound l6-A. In

in which a. R R R R R R R and R were as in the Compound l2-B from which the particular Compound l5-A was prepared; b. A was and propionate) was replaced with a large number of polythiols having at least two -SH groups per'molecule and including ethylene glycol (B -mercaptopropionate), propylene glycol ([3 -mercaptopropionate), and the polythiols disclosed in U.S. Pat. No. 3,615,450 (Werber et al, 96/351) the equivalent ratio of CH ==CH groups of the TADEDS or a Compound l6-A to SH groups varied over the range of l:0.8-l.2. In each instance the results were indistinguishable from those of Example 4.

In other runs using the general procedure of Examples 4 and 17 the benzophonone was replaced with the UV sensitizers (photoinitiators) recited in the aforesaid Werber et a1 patent and the amounts of said photointiators recited in said Werber et al patent. In each instance the results were indistinguishable from those of Examples 4 and 17.

In still other runs the general procedures of Examples 4 and 17 were repeated. However in these runs the fillers of the aforesaid Werber et al. patent (in the quantities taught by said patent) were incorporated into and admixed with the mixtures of TADEDS and polythiol (or Compound l6-A and polythiol) before applying said mixtures to the laminated offset blanket carcasses. In each instance the'results were indistinguishable from those of Example 4.

In other runs using the general procedure of Example 4 and Example 17 the procedure was modified by incorporating into and admixing with the mixtures of TADEDS and polythiol (or Compound l6-A and polythiol) the pigments, odor masks, light-scattering agents, plasticizers and antioxidants of said Werber et al patent in the quantities taught by said patent. In each instance the results were substantially indistinguishable from those of Example 4.

We have found that radiation (light) having a wavelength of 2,000-4,000A is excellently adapted for curing compositions comprising TADEDS and a polythiol (ora Compound 16-A and a polythiol).

In another series of runs the general procedure of Examples 4 and 17 were repeated. However in each of these runs the benzophenone was omitted and the acetone solution of TADEDS and pentaerythritol tetrakis (B-mercaptopropionate) or the acetone solution of a Compound 16-A and pentaerythritol (B-mercapotpropionate) was applied to an aluminum surface and, after drying (evaporating the acetone therefrom), cured by radiation with a high energy ionizing radiation (an electron beam). The effective radiation dosage used were 0.5-30 megarads preferably 2-l0 megarads. The cured coating was a hard protective coating firmly bonded to the metal.

In other instances the electron beam was replaced with; (a) an X-ray beam; and (b) a beam of neutrons. Both the X-ray beam and the beam of neutrons at dosage levels of O.530 megarads gave a hard protective coating of cured polymer firmly bonded to the aluminum surface.

In another series of runs the general procedure of Examples 4 and 17 were repeated. However in each of these runs the benzophenone was omitted and the acetone solution of TADEDS and pentaerythritol tetrakis (3-mercaptopropionate) or the acetone solution of a Compound l6-A and pentaerythritol (3-mercaptoprofonom l I pionate) was admixed with an amount of a peroxide catalyst effective to produce crosslinking and coated onto an aluminum surface. The acetone was evaporated therefrom, and in each instance the coating cured forming a hard protective coating firmly bonded to the aluminum. Peroxides used with excellent results included cumyl peroxide, methylethylketone peroxide. 1,2-peroxycyclopentane,

pound l6-A) is a free radical curable composition. We

prefer to refer to our free radical curable compositions as curable compositions. The free radicals for curing such compositions can be generated by actinic light (preferably having a wave length of ca. 200-4,000A), by high energy ionizing radiation, or by a free radical generating peroxide.

As used herein, the term lower alkyl group means an alkyl group having l-7 carbon atoms.

As used herein, the term mole" has its generally accepted meaning-a mole of a substance being that quantity of the substance which contains the same number of molecules of the substance as there are atoms of carbon in 12 g of pure C.

As used herein, the term g means gram (or grams).

The term mil, was used herein, means 0.001 inch.

The term as used herein, means parts per hundred, and the term parts means parts by weight unless otherwise defined where used.

The term ml as used herein means milliliter (0.001 liter).

As applied to TADEDS or to any Compound l6-A the term equivalent means that quantity of TADEDS or said Compound l6-A which contains one -CH=CH group (i.e., 27.0 g of the CI-I=CH group); /1 mole of TADEDS or a Compound l6-A is an equivalent of TADEDS or the Compound 16-A.

As applied to a polythiol the term equivalent means that quantity of the polythiol which contains one SI-I group (i.e., 33.1 g of SI-I group); A mole of pentaerythritol tetrakis (3-mercaptopropionate) is an equivalent, and one-third mole of trimethylol-propane tris (thioglycolate) is an equivalent.

We claim:

I. A compound having the formula R2 R1 R1 R: R; Ru i I i i /CII:CII CII2 @-o solN i CIMCII UII: Ra R4 R1 R1 R5 R R6 R R2 R1 R1 R2 R1, Rn mc cficge I l I l I f n-It'll (III,-

Nois -o- *o SIM-N or 5 1130:011011-1 I l I (II-:(II (u- R7 R5 R1! R4 R Rt Rs ll:

in which: in which:

h 2, R R R R R and R are independently a. A is SO -RSO selected from the group consisting of hydrogen, and fluorine, chloride, bromine, and lower alkyl; R 18 b. A 18 6 I, I I

s OzNRN02S; l5 IIN@NII,

l I n IIN H NH,

l 11 x l HNCHz@CHz-NII,

' I{N -c1r2-N1r, an alkylene group having 2-20 carbon atoms, a cycloalkylene group having 3-10 carbon atoms, or a phenylene group; and

l (1. R and R are independently selected from a IUlPCHZCHTNH rou consisting of hydrogen, lower alkyl, a cyclo- I lkyl group having 3-10 carbon atoms, and a phe- HN@CH2CHP@ nyl group. 2. The compound of claim 1 in which R R R R.,, H R R R and R are hydrogen. I

3. The compound of claim 2 in which R is I CH3 II OH],

' H 0 4. The compound of claim 2 in which R is an alkyl- 40 ene group having 2-12 carbon atoms.

5. The compound of claim 2 in which R is 2( 2)4 2- 6. A compound having the formula ClhCll' Clla in which: I

a. A is u b. R is H c. R;, R R R R R R and R are independently or CH (CH CH selected from the group consisting of hydrogen,

7. A compound having the formula fluorine, chlorine, bromine and lower alkyl.

" 13; UPDIITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Page 3,856,858 Dated December 24, 1974 Kmrentozfls) hrikant V. Dighe and Richard W. Bush It is certified that error appears in the aboveddentified patent and that said Letters Patent are hereby corrected as shown below:

In the title, Line 2, of Title Page (page bearing the Abstract) change "N,N,N'-TETRA" to N,N,N'N=-TETRA In the title, Line 1 of Column 1, change "N,N,N"-TETRA" to N,N,N'NV'-TEITRA Signed and sealed this 6th day of May 1975..

(SEAL) Attest:

C. MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks 

1. A COMPOUND HAVING THE FORMULA
 2. The compound of claim 1 in which R1, R2, R3, R4, R5, R6, R7, and R8 are hydrogen.
 3. The compound of claim 2 in which R9 is
 4. The compound of claim 2 in which R9 is an alkylene group having 2-12 carbon atoms.
 5. The compound of claim 2 in which R9 is -CH2(CH2)4CH2-.
 6. A compound having the formula
 7. A compound having the formula 